JPH04285607A - Production of ethylene-alpha-olefin copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer having narrow compositional distribution, excellent weather resistance, colorability and strength and high molecular weight by copolymerizing ethylene and an alpha-olefin in the presence of a catalyst system containing a specific Ti amide and an oxygen-containing Al alkyl compound under specific condition. CONSTITUTION:The objective ethylene-alpha-olefin copolymer can be produced by copolymerizing ethylene and an alpha-olefin (e.g. 1-hexene) at a polymerization temperature of >=120 deg.C in the presence of a catalyst system consisting of (A) a titanium amide compound of formula I (R<1> and R<2> are 1-30C hydrocarbon group; Y is alkoxy; 0<=n<=3) [e.g. tetrakis(dimethylamino)titanium] and (B) an oxygen-containing aluminum alkyl compound such as cyclic or linear aluminoxane having the structure of formula II (R<3> is 1-8C hydrocarbon; k is integer of >=1) and formula III.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to a process for producing ethylene-α-olefin copolymers using a novel Ziegler catalyst system. In particular, 1 using a polymerization catalyst consisting of a titanium amide compound and an oxygen-containing aluminum alkyl compound.
The present invention relates to a method for producing an ethylene-α-olefin copolymer at a temperature higher than 20°C. More specifically, by using a new catalyst system, we have developed a catalyst with a narrow composition distribution, high molecular weight, and weather resistance.
The present invention relates to a method for producing an ethylene-α-olefin copolymer having excellent colorability, corrosion resistance, and mechanical properties.

0002

BACKGROUND OF THE INVENTION Olefin copolymers are used in a wide variety of applications, including films, laminates, wire coatings, injection molded products, and special molded products. In each of these applications, it is generally known that in order to obtain excellent transparency, impact resistance, blocking properties, etc., it is better to use a polymer with a narrow molecular weight distribution and composition distribution. In particular, in copolymers, as the content of copolymerized α-olefin increases, the influence of molecular weight distribution and composition distribution on the physical properties of olefin polymers increases, and olefin copolymers with narrow molecular weight and composition distributions It is requested.

[0003] Generally, as a method for producing olefin copolymers, a method using a so-called Ziegler-Natta catalyst consisting of a transition metal compound of Groups IV to VI of the periodic table and an organometallic compound of Groups I to III is widely known. It is being

At present, the following two methods are being used to produce olefin polymers at high temperatures using these Ziegler type catalysts. The first method is generally called a "solution method" and involves polymerizing or copolymerizing olefins using a solvent such as cyclohexane. This method uses a Ziegler-type catalyst to prepare olefins at generally 120-250°C for 5
Polymerization is carried out in a polymer solution state under conditions of ~50 kg/cm2. The second method is generally called the "high-pressure ion method" and involves polymerizing or copolymerizing the olefin in a molten state without a solvent under high temperature and high pressure. These high-temperature solution polymerization methods and high-pressure ionic polymerization methods using Ziegler type catalysts are known to have the advantage of compact reactors and a high degree of freedom in selecting comonomers.

[0005] Various improvements have been made to the Ziegler type solid catalyst for high temperatures (for example, Japanese Patent Application Laid-Open Nos. 144397-1982, 52192-1982, and 18607-1980). , Japanese Patent Publication No. 56-9
9209, JP 57-87405, JP 57-153007, JP 57-19000
No. 9, JP-A No. 58-208803), these all have a wide composition distribution, and have not been able to obtain satisfactory transparency and mechanical properties.

On the other hand, as a method for obtaining an olefin polymer having a narrow molecular weight distribution and composition distribution, a method is known in which an olefin is polymerized using a catalyst formed from a vanadium-based catalyst component and an organoaluminum compound catalyst component.
It has the disadvantage that the activity per transition metal is low, and the activity becomes even lower when polymerized at a high temperature of 120° C. or higher. In order to solve these problems, methods using a catalyst system consisting of a titanium compound or a zirconium compound and an aluminum compound have been disclosed. In particular, recently, a method using a catalyst system consisting of a titanium compound or a zirconium compound and aluminoxane has been disclosed. Proposed. (Special table Hei 1-50
(No. 3788, Japanese Patent Application Laid-open No. 62-121708) However, when this catalyst system is used in a high-temperature solution method, the resulting copolymer has a low molecular weight, so it cannot be said that it is necessarily satisfactory in terms of practical physical properties. Furthermore, the copolymerizability of α-olefins is not sufficient, and a larger amount of expensive α-olefins is required in the polymerization system, which is not economically preferable.

[0007] Furthermore, as a method for polymerizing or copolymerizing olefins using a catalyst system consisting of a compound having a titanium nitrogen bond and an organoaluminum compound, a method for polymerizing or copolymerizing an olefin using a catalyst system consisting of a titanium amide compound supported on magnesium halide and an organoaluminum compound is known. A method using a catalyst system (EP
0320169, Italian Patent No. 867243), a method using a catalyst system consisting of a titanium diphenylamide compound and an organoaluminum compound (EP010
4374, Japanese Patent Publication No. 42-11646), a method using a catalyst system consisting of a titanium amide compound having an aryl substituent and an organoaluminum compound (Japanese Patent Publication No. 42-11646);
-22691), and a method using a catalyst system consisting of a titanium amide compound having a lower alkyl group such as dimethylamide titanium trichloride and an organic aluminium compound (J. of Polym. Sci. Pa
rtA-1, 241, 6 (1968)) and the like have been proposed.

However, even if ethylene and α-olefin are copolymerized using the catalyst systems disclosed in these publications, the methods disclosed in, for example, EP 0320169 and Italian Patent No. 867243, the resulting ethylene- The composition distribution of the α-olefin copolymer is wide, and EP0104374, Japanese Patent Publication No. 42-11646
No. 1, Japanese Patent Publication No. 42-22691, and J. o
f Polym. Sci. Part A-1, 241,
6 (1968) etc. have not yet been satisfactory in terms of catalytic activity, copolymerizability, and narrow composition distribution.

In order to solve these problems, the present inventors first developed (A) the general formula (R1 R2 N) 4-
(m+n) TiXm Yn [However, R1 and R2
is a saturated hydrocarbon group having 8 to 30 carbon atoms, X is halogen, Y
is an alkoxy group, m is a number of 1≦m≦3, n is a number of 0≦n≦2, and (m+n) is 1≦(m+n)≦3. ]
A method for producing a copolymer with a narrow composition distribution in the copolymerization of ethylene and α-olefin by using a catalyst system comprising a liquid catalyst component characterized by comprising a titanium compound represented by the formula and an organic aluminum compound. (Japanese Patent Application Laid-Open No. 2-77412).

However, in this production method, when the catalyst system was used for polymerization under high temperature conditions, the catalytic activity was very low, the copolymerizability with α-olefin was poor, and the composition distribution was not satisfactory. .

[0011]

[Problem to be solved by the invention] In this current situation,
The problem to be solved by the present invention, or the purpose of the present invention, is to use a new catalyst system that has high activity per transition metal under high temperature conditions, has a narrow composition distribution, has a high molecular weight, has good weather resistance, has no coloration, An object of the present invention is to provide a method for producing an ethylene-α-olefin copolymer having excellent corrosion resistance and mechanical properties.

0012

[Means for Solving the Problems] The present invention provides (A) general formula (R1 R2 N) 4-n TiYn (where R1 and R2 are hydrocarbon groups having 1 to 30 carbon atoms, Y is an alkoxy group, and n is 0≦n≦3) Using a catalyst system consisting of a titanium amide compound represented by (0≦n≦3) and (B) an oxygen-containing aluminum alkyl compound, ethylene and α-olefin are synthesized at a polymerization temperature higher than 120°C. The present invention relates to a method for producing an ethylene-α-olefin copolymer characterized by copolymerization. The present invention will be explained in detail below.

Catalyst component (A) used in the present invention
is composed of a nitrogen-containing titanium compound represented by the general formula (R1 R2 N)4-n TiYn. (R
1 and R2 are hydrocarbon groups having 1 to 30 carbon atoms and may be the same or different, and Y is an alkoxy group. n represents a number of 0≦n≦3. ) R1 and R2 are not particularly limited, and the catalyst component (A) may be in a solid state or a liquid state. In addition, alkoxy groups include methoxy, ethoxy,
Examples include propoxy, butoxy, 2-ethylhexoxy groups, etc., but there are no particular limitations from the point of view of catalytic performance.

The following preferred titanium amide compound (A
) Specific examples include tetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium,
Tetrakis (dipropylamino) titanium, Tetrakis (dibutylamino) titanium, Tetrakis (dihexylamino) titanium, Tetrakis (diphenylamino) titanium, Tetrakis (dioctylamino) titanium, Tetrakis (didecylamino) titanium, Tetrakis (dioctadecylamino) titanium, Methoxytris (dimethylamino) titanium, ethoxytris (dimethylamino) titanium, butoxytris (dimethylamino) titanium, hexoxytris (dimethylamino) titanium, 2-ethylhexoxytris (dimethylamino) titanium, decoxytris (dimethylamino) titanium ) Titanium, methoxytris (diethylamino) titanium, ethoxytris (diethylamino)
Titanium, butoxytris (diethylamino) titanium, hexoxytris (diethylamino) titanium, 2-ethylhexoxytris (diethylamino) titanium, decoxytris (diethylamino) titanium, methoxytris (dipropylamino) titanium, ethoxytris (dipropylamino) titanium, Butoxytris (dipropylamino) titanium, hexoxytris (dipropylamino) titanium, 2-ethylhexoxytris (dipropylamino) titanium, decoxytris (dipropylamino) titanium, methoxytris (dibutylamino) titanium, ethoxytris (dibutyl) amino) titanium, butoxytris (dibutylamino) titanium, hexoxytris (dibutylamino) titanium, 2-ethylhexoxytris (dibutylamino) titanium, decoxytris (dibutylamino) titanium, methoxytris (dihexylamino) titanium, ethoxytris (dihexyl) amino)
Titanium, butoxytris (dihexylamino) titanium, hexoxytris (dihexylamino) titanium, 2-ethylhexoxytris (dihexylamino) titanium, decoxytris (dihexylamino) titanium, methoxytris (diphenylamino) titanium, ethoxytris (diphenylamino) titanium Titanium, butoxytris(diphenylamino)titanium, hexoxytris(diphenylamino)titanium, 2-
Ethylhexoxytris(diphenylamino)titanium, decoxytris(diphenylamino)titanium,
Methoxytris (dioctylamino) titanium, ethoxytris (dioctylamino) titanium, butoxytris (dioctylamino) titanium, hexoxytris (didecylamino) titanium, 2-ethylhexoxytris (didecylamino) titanium, decoxytris (dioctylamino) titanium, methoxytris (didecylamino) titanium, ethoxytris (didecylamino) titanium, butoxytris (didecylamino) titanium, hexoxytris (didecylamino) titanium, 2-ethylhexoxytris (didecylamino) titanium, decoxytris (didecylamino) titanium, tris (dioctadecylamino) titanium, Ethoxytris (dioctadecylamino) titanium, butoxytris (dioctadecylamino) titanium, hexoxytris (dioctadecylamino) titanium, 2-ethylhexoxytris (dioctadecylamino) titanium, decoxytris (dioctadecylamino) titanium, etc. Can be done. Among these, particularly preferred are tetrakis(dimethylamino)titanium, tetrakis(diethylamino)titanium,
Tetrakis (dipropylamino) titanium, tetrakis (dibutylamino) titanium, tetrakis (dihexylamino) titanium, tetrakis (diphenylamino) titanium, tetrakis (dioctylamino) titanium, tetrakis (didecylamino) titanium, tetrakis (dioctadecylamino) titanium, etc. can be exemplified.

The method for synthesizing the titanium amide compound (A) is described in Japanese Patent Publication No. 41-5397 and Japanese Patent Publication No. 42-5397.
-11646 publication, H. Burger et. al
．． J. of Organomet. Chem. 108
(1976), 69-84, H. Burger et.
al J. of Organomet. Che
m. 20 (1969), 129-139, etc. can be used.

In the present invention, according to these methods, (i) a secondary amine compound represented by the general formula R4 R5 NH (R4 and R5 are hydrocarbon groups having 1 to 30 carbon atoms); and (ii) R6 M ( R6 represents a hydrocarbon group having 1 to 30 carbon atoms, M represents an alkali metal such as Li or K, etc.) to synthesize an alkali metal amide compound; , (iii) Synthesis was performed by reacting titanium tetrahalide represented by the general formula TiX4 (X is a halogen such as chlorine, bromine, or iodine, and preferably chlorine).

In the present invention, component (B) for polymerization catalyst
The oxygen-containing aluminum alkyl compound used as has the general formula [Al(R3)-O]k and R32
Al[Al(R3)-O]k AlR3 2
(However, R3 is a hydrocarbon group having 1 to 8 carbon atoms, and k is an integer of 1 or more.) Cyclic and chain aluminoxanes having the structure shown can be exemplified. Specific examples include tetramethyldialuminoxane, tetraethyldialuminoxane, tetrabutyldialuminoxane, tetrahexyldialuminoxane, methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, and the like. Particularly preferred is methylaluminoxane.

Aluminoxanes are produced by various methods. Preferably they are made by contacting water with a solution of a trialkylaluminium, such as trimethylaluminum, in a suitable organic solvent such as toluene or an aliphatic hydrocarbon. For example, the aluminum alkyl is treated with water in the form of a wet solvent. In another method, it may be desirable to be able to contact an aluminum alkyl, such as trimethylaluminum, with a hydrated salt, such as hydrated copper sulfate or ferrous sulfate. Preferably, the aluminoxane is made in the presence of hydrated ferrous sulfate. This method prepares a dilute solution of trimethylaluminum, for example in toluene, with the general formula FeSO4 7H2
ferrous sulfate represented by O. Preferably, the ratio is about 1 mole of ferrous sulfate to 6 to 7 moles of trimethylaluminum. The reaction is evidenced by the evolution of methane.

Component (B) can be used in a wide range of amounts, such as from 1 to 10,000 mol, preferably from 1 to 1,000 mol, more preferably from 1 to 500 mol, per mol of titanium atoms in component (A). Used in molar range.

In the present invention, there are no particular restrictions on the method of supplying each catalyst component to the polymerization tank, except that it is supplied in an inert gas such as nitrogen or argon without moisture. Catalyst components (A) and (B) may be supplied individually or may be supplied in contact with each other in advance.

[0021] The polymerization conditions in the present invention are 120°C or higher;
Preferably 135°C to 350°C, more preferably 150°C
The temperature and pressure are 5 to 10 degrees Celsius to 270 degrees Celsius in the case of solution method.
0kg/cm2, preferably 10-50kg/cm2
, 350 to 3500 kg/c in the case of high pressure ion method
m2, preferably 700 to 1800 kg/cm2, and the polymerization method can be either batchwise or continuous.

In the solution method polymerization using the catalyst system of the present invention, the solvent is generally selected from hydrocarbon solvents such as hexane, cyclohexane, heptane, kerosene components, toluene, and the like.

The α-olefin used in the present invention is an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Examples include propylene, 1-butene, 1-4-methylpentene, 1-hexene, 1-octene, and vinylcyclohexane. And, the present invention
Ethylene containing at least 80 mol% ethylene and other α-olefins, especially propylene, butene-1, 4
- It can be particularly effectively applied to the production of copolymers with α-olefins such as methylpentene-1, hexene-1, and octene-1. It is also possible to add chain transfer agents such as hydrogen to adjust the molecular weight of the polymer.

[0024]

[Examples] The present invention will be explained in more detail below with reference to Examples and Comparative Examples. The properties of the polymers in the Examples were measured by the following methods. The α-olefin content was determined by the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (manufactured by JASCO Corporation) JASCO-302. The intrinsic viscosity [η] is determined using an Ubbelohde viscometer.
Measurements were made in a tetralin solution at 5°C. As a measure representing the composition distribution, the average melting point <Tm> was determined by the following formula using a differential scanning calorimeter (DSC). The smaller the value of <Tm>, the narrower the composition distribution. (50℃<ti<130℃, Hi is the melting energy (W/g) at temperature ti)

Example 1 (1) Synthesis of catalyst component Synthesis of titanium amide compound (A): After purging a 300 ml flask equipped with a stirrer, dropping funnel, and thermometer with argon, 18.1 ml (60 ml) of dioctylamine was added. mmol) and 150 ml of hexane were charged. Next, 38.7 ml (60 mmol) of butyl lithium diluted with hexane was added dropwise from the dropping funnel over 30 minutes while keeping the temperature of the solution in the flask at 5°C.
The reaction was further carried out at 30°C for 2 hours. Next, 1.65 ml (15 mmol) of TiCl4 diluted with hexane was added from the dropping funnel into the mixture obtained in the above reaction at a temperature of 5°C.
After the dropwise addition, the reaction was further carried out at 5°C for 1 hour and at 30°C for 2 hours.
H17) 15 mmol (assuming a yield of 100%) of a titanium amide compound (A) represented by 2N]4Ti was obtained. (Catalyst concentration 0.062 mmol.Ti/ml) (2) Ethylene polymerization An autoclave equipped with a stirrer with an internal volume of 400 ml was vacuum dried and replaced with argon, and then toluene 14
0ml, 1-hexene 480mm as α-olefin
The reactor was heated to 180°C. After raising the temperature, feed the ethylene while adjusting the pressure to 25 kg/cm2, and after the system becomes stable, 8 mm of methylaluminoxane (MAO) manufactured by Tosoh Akzo Co., Ltd. is added as an organic aluminum compound.
ol, and then the catalyst synthesized in (1) above [(C
8H17) 0.08 mmol of 2N]4Ti was added. Polymerization was carried out for 2 minutes while controlling the temperature to 180°C. As a result of polymerization, 22,000 per mol of transition metal
g copolymer (activity -22,000 g-coply/m
ol・M) was obtained. The results are shown in Table 1. Furthermore, a diagram of the melting behavior of the obtained copolymer measured by DSC is shown in FIG. In FIG. 1, the horizontal axis represents temperature (°C), and the vertical axis represents melting energy (μw). In FIG. 1, it can be said that the composition distribution is narrower so that the melting peak is observed in the low temperature measurements. The composition distribution of the obtained copolymer was very narrow.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that 8 mmol of triisobutylaluminum (TIBA) was added instead of MAO as an organic aluminum compound during the polymerization of ethylene in Example 1 (2). I did it. As a result of polymerization, almost no polymer was obtained.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that 8 mmol of ethylaluminum dichloride (EADC) was added instead of MAO as an organic aluminum compound during the polymerization of ethylene in Example 1 (2). I did it. As a result of the polymerization, 31,000 g of polymer was obtained per mol of transition metal, and the molecular weight of the polymer was [η] = 0.04.
This was much lower than in Example 1.

Comparative Example 3 An autoclave equipped with a stirrer having an internal volume of 400 ml was vacuum-dried and replaced with argon, and 140 ml of toluene was added as a solvent.
ml, 1-hexene 480 mmo as α-olefin
1 was charged, and the temperature of the reactor was raised to 80°C. After raising the temperature, feed ethylene while adjusting the pressure to 6.0 kg/cm2, and after the system becomes stable, MAO is added as an organic aluminum compound.
8 mmol was added, followed by 0.08 m of the catalyst [(C8 H17) 2 N] 4 Ti synthesized in Example 1 (1).
mol was added. Polymerization was carried out for 2 minutes while controlling the temperature to 80°C. As a result of polymerization, almost no polymer was obtained.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was 200° C. during the polymerization of ethylene in Example 1 (2). Similar to Example 1, a polymer with a narrow composition distribution was obtained.

Comparative Example 4 Biscyclopentadienylzirconium dichloride (
Polymerization was carried out in the same manner as in Example 2, except that 0.08 mmol of Cp2ZrCl2) was used. As a result of the polymerization, the molecular weight of the obtained polymer was [η]=0.17, which was much lower than that of Example 2.

Comparative Example 5 (1) Synthesis of catalyst component Synthesis of titanamide compound: After purging a 100 ml flask equipped with a stirrer, dropping funnel, and thermometer with argon, 6.0 ml (20 mmol) of dioctylamine, 50 ml of hexane was charged. Next, 12.9 ml (20 mmol) of butyl lithium diluted with hexane was added from the dropping funnel for 3 hours while keeping the temperature of the solution in the flask at 5°C.
After dropping for 0 minutes, at 5℃ for 2 hours, and at 30℃ for 2 hours.
The reaction was carried out for an additional hour. Next, Ti diluted with hexane
2.2 ml (20 mmol) of Cl4 was added from the dropping funnel into the mixture obtained in the above reaction for 3 minutes while keeping the temperature at 5°C.
After dropping for 0 minutes, at 5℃ for 1 hour, and at 30℃ for 2 hours.
The reaction was further carried out for an additional period of time, and the composition formula (C8 H17) 2
20 mmol (assuming a yield of 100%) of a titanium amide compound represented by NTiCl3 was obtained. (2) Polymerization of ethylene In Example 1 (2), the catalyst [(C8 H17) 2
N]4 Instead of Ti, the catalyst synthesized in (1) above (
C8 H17) 2 NTiCl3 0.08 mmol
Polymerization was carried out in the same manner as in Example 1 (2) except that . The results are shown in Table 1. The composition distribution of the obtained polymer was wide.

Comparative Example 6 In Comparative Example 5, TIBA was used instead of MAO as the organic aluminum compound during the polymerization of ethylene in Comparative Example 5 (2).
Polymerization was carried out in the same manner as in Comparative Example 5 except that 8 mmol was added. The polymerization results are shown in Table 1. The polymerization activity was very low, and the composition distribution of the obtained polymer was wide.

Comparative Example 7 In Example 1, during the ethylene polymerization of Example 1 (2),
[(C8 H17) 2 N] 4 Ti as a catalyst component
Polymerization was carried out in the same manner as in Example 1, except that 0.08 mmol of TiCl4 was used instead of. The polymerization results are shown in Table 1, and the measurement diagram by DSC is shown in FIG. 2. the result,
Copolymerizability was poor, and the composition distribution of the resulting polymer was wide.

Comparative Example 8 (1) Synthesis of catalyst components After purging a 100 ml flask equipped with a stirrer, dropping funnel, and thermometer with argon, 3.8 g of decyl alcohol was added.
ml (20 mmol) and 50 ml of hexane were charged. Next, 12.9 ml of butyllithium diluted with hexane
(20 mmol) was added dropwise from the dropping funnel over 30 minutes while keeping the temperature of the solution in the flask at 5°C, and after completion of the dropwise addition, the reaction was further carried out at 5°C for 2 hours and at 30°C for 2 hours. Next, 0.55 ml (5 ml) of TiCl4 diluted with hexane
mmol) was added dropwise from the dropping funnel into the mixture obtained in the above reaction over 30 minutes while keeping the temperature at 5°C. After the addition, the reaction was further carried out at 5°C for 1 hour and at 30°C for 2 hours. 5 mmol (assuming a yield of 100%) of a titanium compound represented by (C10H21O)4Ti was obtained. (2) Ethylene polymerization In Example 1, during the ethylene polymerization of Example 1 (2),
[(C8 H17) 2 N] 4 Ti as a catalyst component
Instead of the catalyst synthesized in (1) above (C10H21O
)4 Polymerization was carried out in the same manner as in Example 1 except that Ti was used. The polymerization results are shown in Table 1, and the measurement diagram by DSC is shown in FIG. 3. The activity per transition metal was lower than in Example 1, and the composition distribution of the obtained polymer was also wide.

Example 3 (1) Synthesis of catalyst component Synthesis of titanium amide compound (A): After purging a 300 ml flask equipped with a stirrer, dropping funnel, and thermometer with argon, 6.3 ml (60 mmol of diethylamine) was added. )
, 150 ml of hexane was charged. Next, 38.7 ml (60 mmol) of butyl lithium diluted with hexane was added dropwise from the dropping funnel over 30 minutes while keeping the temperature of the solution in the flask at 5°C.
The reaction was further carried out at ℃ for 2 hours. Next, 1.65 ml (15 mmol) of TiCl4 diluted with hexane was added dropwise from the dropping funnel into the mixture obtained in the above reaction over 30 minutes while keeping the temperature at 5°C, and after the dropwise addition was completed, it was kept at 5°C for 1 hour. ,
The reaction was further carried out at 30°C for 2 hours, and the composition formula [(C2H
5) 15 mmol (assuming a yield of 100%) of a titanium amide compound (A) represented by 2N]4Ti was obtained. (2) Polymerization of ethylene In Example 1 (2), [(C8H
17) Instead of 2N]4Ti, the catalyst synthesized in (1) above [(C2H5)2N]4Ti0.0
Polymerization was carried out in the same manner as in Example 1 (2) except that 8 mmol was used. Similar to Example 1, a polymer with a narrow composition distribution was obtained.

Comparative Example 9 In Example 3, TIBA8 was used instead of MAO as the organic aluminum compound during the polymerization of ethylene in Example 3 (2).
Polymerization was carried out in the same manner as in Example 3 except that mmol was added. As a result of polymerization, almost no polymer was obtained.

Comparative Example 10 (1) Synthesis of catalyst component Synthesis of titanium amide compound: After purging a 100 ml flask equipped with a stirrer, dropping funnel, and thermometer with argon, 2.1 ml (20 mmol) of diethylamine and hexane were added. 50 ml was charged. Next, 12.9 ml (20 mmol) of butyllithium diluted with hexane was added through the dropping funnel for 30 minutes while keeping the temperature of the solution in the flask at 5°C.
After the dropwise addition was completed, the reaction was carried out at 5°C for 2 hours and then at 30°C for 2 hours. Next, Ti diluted with hexane
2.2 ml (20 mmol) of Cl4 was added from the dropping funnel into the mixture obtained in the above reaction for 3 minutes while keeping the temperature at 5°C.
After dropping for 0 minutes, at 5℃ for 1 hour, and at 30℃ for 2 hours.
The reaction was carried out for an additional hour. After the reaction, the mixture was allowed to stand, fixed and separated, and then washed twice with 50 ml of hexane. After drying under reduced pressure, 4.5 g of a solid titanamide compound represented by the composition formula (C2 H5)2 NTiCl3 was obtained. (2) Polymerization of ethylene In Example 1 (2), [(C8H
17) Instead of 2N]4Ti, the catalyst synthesized in (1) above (C2H5)2NTiCl3 0.08
Polymerization was carried out in the same manner as in Example 1 (2) except that mmol was used. The composition distribution of the obtained polymer was wide.

Comparative Example 11 In Comparative Example 10, during the polymerization of ethylene in Comparative Example 10(2), T was used instead of MAO as the organic aluminum compound.
Polymerization was carried out in the same manner as in Comparative Example 10, except that 8 mmol of IBA was added. The polymerization results are shown in Table 1. The polymerization activity was very low, and the composition distribution of the obtained polymer was wide.

Comparative Example 12 (1) Synthesis of catalyst component Synthesis of titanium amide compound: After purging a 200 ml flask equipped with a stirrer, dropping funnel, and thermometer with argon, 2.7 g (16 mmol) of diphenylamine and hexane were added. 100ml was charged. Next, 10.3 ml (16 mmol) of butyl lithium diluted with hexane was added from the dropping funnel to the flask for 3 hours while keeping the temperature of the solution in the flask at 5°C.
After dropping for 0 minutes, at 5℃ for 2 hours, and at 30℃ for 2 hours.
The reaction was carried out for an additional hour. Next, T diluted with hexane
1.76 ml (16 mmol) of iCl4 was added dropwise from the dropping funnel to the mixed solution obtained in the above reaction over 30 minutes while keeping the temperature at 5°C, and after the dropwise addition was completed, the temperature was kept at 5°C for 1 hour, then at 30°C.
The reaction was further carried out for 2 hours, and the composition formula (C6 H5)2
Titanium amide compound 16 represented by NTiCl3
mmol (assuming 100% yield) was obtained. (2) Polymerization of ethylene In Example 1 (2), [(C8H
17) Instead of 2N]4Ti, the catalyst synthesized in (1) above (C6H5)2NTiCl3 0.08
Polymerization was carried out in the same manner as in Example 1 (2) except that 8 mmol of triethylaluminum (TEA) was used instead of MAO as the organic aluminum compound. The polymerization results are shown in Table 1. The polymerization activity was very low, and the composition distribution of the obtained polymer was wide.

Example 4 (1) Synthesis of catalyst component Synthesis of titanium amide compound (A): After purging a 300 ml flask equipped with a stirrer, dropping funnel, and thermometer with argon, 2.7 g (16 mmol) of diphenylamine was added. )
, 200 ml of hexane was charged. Next, 10.3 ml (16 mmol) of butyllithium diluted with hexane was added dropwise from the dropping funnel over 30 minutes while keeping the temperature of the solution in the flask at 5°C.
The reaction was further carried out at ℃ for 2 hours. Next, 0.44 ml (4 mmol) of TiCl4 diluted with hexane was added dropwise from the dropping funnel into the mixture obtained in the above reaction over 30 minutes while keeping the temperature at 5°C, and after the dropwise addition was completed, it was kept at 5°C for 1 hour. ,3
The reaction was further carried out at 0°C for 2 hours, and the composition formula [(C6 H5
4 mmol (assuming a yield of 100%) of a solid titanamide compound (A) represented by )2N]4Ti was obtained. (2) Polymerization of ethylene In Example 1 (2), [(C8H
17) Instead of 2N]4Ti, the catalyst synthesized in (1) above [(C6H5)2N]4Ti0.08
Polymerization was carried out in the same manner as in Example 1 (2) except that mmol was used. Similar to Example 1, a polymer with a narrow composition distribution was obtained.

Comparative Example 13 Polymerization was carried out in the same manner as in Example 4, except that 8 mmol of diethylaluminium chloride (DEAC) was added instead of MAO as an organic aluminum compound during the polymerization of ethylene in Example 4 (2). I did it. The polymerization results are shown in Table 1. The polymerization activity was very low compared to Example 4, and the composition distribution of the obtained polymer was also wide.

Example 5 (1) Synthesis of catalyst component Synthesis of titanium amide compound (A): After purging a 300 ml flask equipped with a stirrer, dropping funnel, and thermometer with argon, 10.5 ml (60 ml) of diisobutylamine was added. mmol) and 150 ml of hexane were charged. Next, 38.7 ml (60 mmol) of butyl lithium diluted with hexane was added dropwise from the dropping funnel over 30 minutes while keeping the temperature of the solution in the flask at 5°C. The reaction was further carried out for 2 hours. Next, 1.65 ml (15 mmol) of TiCl4 diluted with hexane
from the dropping funnel into the mixture obtained in the above reaction at a temperature of 5.
Drop it for 30 minutes while keeping the temperature at 5°C.
The reaction was further carried out at 30°C for 2 hours, and the composition formula {[(
15 mmol (assuming a yield of 100%) of a titanium amide compound (A) represented by CH3)2CHCH2]2N}4Ti was obtained. (2) Polymerization of ethylene In Example 1 (2), [(C8H
17) Instead of 2N]4Ti, the catalyst synthesized in (1) above {[(CH3)2CHCH2]2N
}4 Example 1 except that 0.08 mmol of Ti was used (
Polymerization was carried out in the same manner as in 2). Similar to Example 1, a polymer with a narrow composition distribution was obtained.

Comparative Example 14 (1) Synthesis of catalyst component Synthesis of titanium amide compound: After purging a 300 ml flask equipped with a stirrer, dropping funnel, and thermometer with argon, 0.41 ml (10 mmol) of methyl alcohol,
25 ml of hexane was charged. Next, 6.5 ml (10 mmol) of butyllithium diluted with hexane was added from the dropping funnel to the flask for 3 hours while keeping the temperature of the solution in the flask at 5°C.
After dropping for 0 minutes, at 5℃ for 2 hours, and at 30℃ for 2 hours.
The reaction was carried out for an additional hour. Next, (C8 H17) 2 NTiCl3 was synthesized in the same manner as in Comparative Example 5 (1).
10 mmol was added dropwise from the dropping funnel into the liquid mixture obtained in the above reaction over 30 minutes while keeping the temperature at 5°C, and after the dropwise addition was completed, the reaction was further carried out at 5°C for 1 hour and at 30°C for 2 hours, and the composition formula ( C8 H17) 2 NTi(OCH3)
10 mmo of titanium amide compound represented by Cl2
1 (assuming a yield of 100%). (2) Polymerization of ethylene In Example 1 (2), [(C8H
17) Instead of 2N]4Ti, the catalyst synthesized in (1) above (C8H17)2NTi(OCH3)
Example 1 except that 0.08 mmol of Cl2 was used (
Polymerization was carried out in the same manner as in 2). The composition distribution of the obtained polymer was wide.

Example 6 Using the same catalyst system as in Example 1, ethylene and 1-butene were copolymerized. Similar to Example 1, a polymer with a narrow composition distribution was obtained.

Example 7 Using the same catalyst system as in Example 1, ethylene and 4-methyl-pentene-1 were copolymerized. Similar to Example 1, a polymer with a narrow composition distribution was obtained.

Example 8 Using the same catalyst system as in Example 1, ethylene and 1-decene were copolymerized. Similar to Example 1, a polymer with a narrow composition distribution was obtained. The polymerization conditions and polymerization results for the above examples are summarized in Table 1.

[0047]

Actual Example Ratio Comparative Example Polymerization temperature: 180°C (However, Ratio 3 is 80°C, Actual
2 and ratio -4 at 200 °C) MAO: methylaluminoxane TIBA: triisobutylaluminum EADC: ethylaluminum dichloride TEA: triethylaluminum DEAC: diethylaluminum chloride

0049
]

Effects of the Invention In the olefin polymerization method of the present invention, productivity is improved due to the high catalyst activity per transition metal, and ethylene-α-
Olefin copolymers can be produced, and ethylene/α-olefin copolymers with excellent weather resistance, colorability, corrosion resistance, and mechanical properties can be provided.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the melting behavior of the copolymer obtained in Example 1 measured by differential scanning calorimetry (DSC).

FIG. 2 is a diagram showing the melting behavior of the copolymer obtained in Comparative Example 7 measured by DSC.

FIG. 3 is a diagram showing the melting behavior of the copolymer obtained in Comparative Example 8 measured by DSC.

FIG. 4 is a flowchart diagram to help understand the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited thereto.

Claims (3)

[Claims] Claim 1: (A) General formula (R1 R2 N) 4-n
TiYn (wherein R1 and R2 are hydrocarbon groups having 1 to 30 carbon atoms, Y is an alkoxy group, and n is a number of 0≦n≦3), and (B) oxygen-containing aluminum alkyl 1. A method for producing an ethylene-α-olefin copolymer, which comprises copolymerizing ethylene and α-olefin at a polymerization temperature of higher than 120° C. using a catalyst system comprising a compound. Claim 2: Oxygen-containing aluminum alkyl compound (B
) is represented by the general formula [Al(R3)-O]k and R3
2 Al[Al(R3) -O]k AlR3 2
The production according to claim 1, wherein the aluminoxane is at least one selected from cyclic and chain aluminoxanes having a structure represented by (where R3 is a hydrocarbon group having 1 to 8 carbon atoms, and k is an integer of 1 or more). Method. 3. The production method according to claim 1, wherein the polymerization temperature is higher than 150°C.